CN101038959A - Method and equipment for preparation of lithium battery diaphragm - Google Patents
Method and equipment for preparation of lithium battery diaphragm Download PDFInfo
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- CN101038959A CN101038959A CNA2007100654299A CN200710065429A CN101038959A CN 101038959 A CN101038959 A CN 101038959A CN A2007100654299 A CNA2007100654299 A CN A2007100654299A CN 200710065429 A CN200710065429 A CN 200710065429A CN 101038959 A CN101038959 A CN 101038959A
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- shower nozzle
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method and device for preparing lithium battery separating membrane. The method includes: 1) based on mass, preparing solvent in following ratio: 70 to 90 % dimethyl acylamide, 10 to 30 % acetone; preparing electro spinning solution of 7 to 10 % polyvinylidene fluoride; 2) the electro spinning solution is filled into a liquid storage groove, in temperature of 30 to 45 DEG C., electric field with field intensity of 1000 to 2000 V/cm is applied between nozzles and joint cylinder, and then the electro spinning solution is sprayed to the joint cylinder by the nozzles to form electro spinning silk membrane; 3) electro spinning temperature is adjusted to control the volatilization speed of the solvent in electro spinning solution, therefore, the electro spinning solution can just form screen membrane as soon as reaching the joint cylinder. The device includes a liquid storage groove, nozzles, joint cylinder and high voltage DC generator; the storage groove is supplied by the nozzles, and the output terminal of the high voltage DC generator is connected to the nozzles, and the joint cylinder is connected to ground terminal. The joint cylinder can rotate about its axes, and the nozzles can reciprocally move along the axes of the joint cylinder. The invention can high effectively produce screen lithium battery separating membrane of large area, low cost, high strength, and can easily control the hole rate of lithium battery separating membrane.
Description
Technical field
The present invention relates to a kind of preparation method and equipment of lithium battery diaphragm, particularly a kind of electrostatic spinning prepares the method and apparatus of high-performance lithium battery micro-pore septum.
Background technology
American Formhals in 1934 at first propose the patent imagination of electrospinning.But electrospinning in the past is single ejecting device.This class device has only the basic research as electrospinning, can not realize industrialization.Because per hour the flow of spinning solution is generally about 20ml/ hour for single shower nozzle, the area that forms film simultaneously also is no more than 200 * 200mm
2Though, can be used for the barrier film of simulated battery, can not satisfy the requirement that lithium battery is produced.In order to make the needs of film industrialization in large quantities and in large area, design the pursuit that many shower nozzles electric spinning equipment is many researchers.The difficult point of many shower nozzles electrospinning system film is that the electrostatic field between the shower nozzle disturbs.So-called electrostatic field disturbs, and is meant that each syringe needle all is in same current potential, and each electrospinning bundle also is in same current potential, takes place to repel mutually.Therefore, can not form uniform film during many shower nozzles electrospinning.
Also must the tool certain mechanical strength as battery diaphragm, but the film that electrostatic spinning makes in the prior art does not have good mechanical strength.Its reason is: 1. because the film that electrospinning obtains is a unrelated non-weaving cloth form film between a kind of fiber; 2. electrospinning fibre limited length, and the fiber molecule degree of orientation is not high.If fiber is formed network structure, the mechanical strength of film can improve a lot.Cancellated formation is a special process condition of electrostatic spinning system film, and it makes and forms bonding point when interweaving between the fiber mutually to strengthen film strength.But the method that does not also have can a production effect good netted lithium battery diaphragm in the prior art.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method that can prepare big, the effective netted lithium battery diaphragm of intensity height, area, and the equipment that is used to prepare this barrier film.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of lithium battery diaphragm may further comprise the steps:
1) preparation electrospinning liquid: prepare solvent by following mass percent: dimethylformamide: 70% ~ 90%; Acetone: 10% ~ 30%; Be that solute adds the above-mentioned solvent for preparing then with the Kynoar, mass concentration is 7% ~ 10%;
2) the electrospinning liquid of preparing in the step 1) is put into reservoir, under 30 ~ 45 ℃ of ambient temperatures, at shower nozzle and connect the electric field that adds 1000 ~ 2000V/cm between the silk tube, utilize shower nozzle that electrospinning liquid is sprayed onto and connect on the silk tube, form the electrospinning cortina connecing on the silk tube;
3) regulate the evaporation rate of solvent in the electrospinning temperature control electrospinning liquid, when electrospinning liquid being arrived connect the silk tube, can form reticular membrane connecing on the silk tube just.
The mass concentration of described electrospinning liquid is 8%.
In described step 2) in, the ambient temperature when keeping spinning is constant, controls the porosity of the lithium battery diaphragm that makes by the ratio between dimethylformamide and the acetone in the adjusting electrospinning liquid solvent.
In described step 2) in, keep the proportions constant between the dimethylformamide and acetone in the electrospinning liquid solvent, control the porosity of the lithium battery diaphragm that makes by the ambient temperature of regulating spinning.
The equipment that is used to prepare lithium battery diaphragm of the present invention comprises reservoir, shower nozzle, connects silk tube and high-voltage D.C. generator; Described reservoir is divided into head tank and Lower tank, links to each other by communicating pipe between described head tank and the Lower tank, and described Lower tank links to each other with described shower nozzle by fluid flow tube; Described shower nozzle has a plurality of, and described a plurality of nozzle tip arrangement become at least one row; The described silk tube of connecing is positioned at position near the spout of shower nozzle, and the orientation of described a plurality of shower nozzles is parallel to a described axis that connects the silk tube; The described silk tube that connects can rotate along its central axis, and described shower nozzle can move back and forth along connecing wire tube shaft line direction; The high-tension current out splice going splice of described high-voltage D.C. generator is connected on described a plurality of shower nozzle, and the described silk tube that connects links to each other with the ground end.
Utilize method and apparatus of the present invention, can prepare the netted lithium battery diaphragm that area is big, cost is low, intensity is high, and the production efficiency height, can control the porosity of the lithium battery diaphragm that makes easily.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 carries out simulated battery result of experiment figure for the lithium battery diaphragm that will utilize the present invention to produce;
Fig. 2 assembles the performance chart of battery of mobile phone experiment for the lithium battery diaphragm that will utilize the present invention to produce;
Fig. 3 is the structure principle chart of a kind of embodiment of the equipment of preparation lithium battery diaphragm of the present invention.
Embodiment
Embodiment one:
Ratio by dimethyl formamide and acetone weight is 7: 3 mixed preparing electrospinning liquid solvents, to be solute with Kynoar (PVdF), with above-mentioned solvent, make mass concentration and be 8% electrospinning liquid, the electrospinning liquid for preparing is put into reservoir, utilize shower nozzle that electrospinning liquid is sprayed onto and connect on the silk tube, connecing the netted barrier film of formation on the silk tube.In spray silk film forming procedure, connecing the electric field that adds 1000V/cm between silk tube and the shower nozzle, ambient temperature is controlled at 30 ℃, the mechanical property of made barrier film such as following table:
| Average thickness (um) | 16.8 |
| Molten point (℃) | 165.5 |
| Width (mm) | 51.9 |
| Tensile strength (MD) (kg/cm 2) | 483.47 |
| Tensile strength (TD) (kg/cm 2) | 499.06 |
| Ductility (MD) (%) | 18.42 |
| Ductility (TD) (%) | 63.50 |
| Puncture intensity (g) | 130.4 |
Embodiment two:
Solution electrostatic spinning system film with PVdF mass concentration 8%, dimethyl formamide is 6: 4 with the ratio of acetone volume, the spinning ambient temperature is respectively 25,30,35,40,45 ℃, electric field strength 1000V/cm, technical process is with embodiment one, and the porosity of prepared film is respectively 20%, 39%, 47%, 64%, 79%.
Embodiment three:
It with the PVdF mass concentration 8% solution electrostatic spinning system film, dimethyl formamide and the score of acetone volume are not 6: 4,7: 3,8: 2,8.5: 1.5, electrospinning silk ambient temperature is controlled at 45 ± 1 ℃, electric field strength 1000V/cm, technical process is with embodiment one, and the porosity of the perforated membrane that makes is respectively 79%, 61%, 45%, 42%.
Embodiment four:
With the PVdF mass concentration is 8% solution electrostatic spinning system film, and dimethyl formamide is 7: 3 with the ratio of acetone, and the electrospinning ambient temperature is controlled at 30 ℃, electric field strength 1000V/cm, technical process is made thickness 10 ± 1 μ m, the lithium battery diaphragm of porosity 38% with embodiment one.
Embodiment five:
With the PVdF mass concentration is 8% solution electrostatic spinning system film, and dimethyl formamide is 7: 3 with the ratio of acetone, and the electrospinning ambient temperature is controlled at 45 ℃, electric field strength 1000V/cm, technical process is with embodiment one, and making thickness is 20 μ m, and porosity is 42% lithium battery diaphragm.
Embodiment six:
With the PVdF mass concentration is 7% solution electrostatic spinning system film, and dimethyl formamide is 9: 1 with the ratio of acetone, and the electrospinning ambient temperature is controlled at 50 ℃, electric field strength 1500V/cm, technical process is with embodiment one, and making thickness is 20 μ m, and porosity is 40% lithium battery diaphragm.
Embodiment seven:
With the PVdF mass concentration is 9% solution electrostatic spinning system film, and dimethyl formamide is 8: 2 with the ratio of acetone, and the electrospinning ambient temperature is controlled at 45 ℃, electric field strength 2000V/cm, technical process is with embodiment one, and making thickness is 23 μ m, and porosity is 40% lithium battery diaphragm.
When development nanofiber lithium battery diaphragm, must select suitable macromolecular material, the present invention has selected Kynoar (PVDF) material.PVDF is a kind of of fluoro containing polymers, has solvent resistance and better intensity and toughness than broad, and it also is the filmogen that electrode of lithium cell is made simultaneously, and PVDF has a kind of special compatibility for the electrolyte of lithium battery.
The parameter of electrospinning process control is a lot, such as the electric field strength that applies, and shower nozzle and the distance that connects a cylinder, the flowing velocity of electrospinning liquid etc.After the system of electrospinning liquid was determined, adjustable parameter was mainly solution concentration and temperature on the technology.Concentration also fibrous root is regulated according to high molecular molecular weight and molecular weight distribution, and temperature will be regulated according to the character of the solvent in the solution.
When constant various adjusting factors, electrospinning fibre average diameter and the relation such as the following table that apply electric field strength:
| E(V/cm) | 1000 | 1300 | 1500 | 1800 | 2000 |
| Fibre diameter (nm) | ～800 | ～500 | ～300 | ～100 | ＜100 |
As the nano fibrous membrane of lithium battery, the diameter of fiber is not needed strict control, in bigger scope, can both be suitable for.Generally fibre diameter is controlled at about 200nm.
In the electrospinning film-forming process, can control the porosity of film forming by the temperature that controls environment, utilize mass concentration (the solvent composition dimethyl formamide wherein: electrospinning liquid system film acetone=6: 4) that is 8%, apply electric field strength 1000V/cm, spray flight lead from 22.5cm, temperature and relation that becomes porosity such as following table:
| Temperature (℃) | 30 | 33 | 35 | 37 | 40 |
| Thickness (μ m) | 22 | 23 | 22 | 31 | 23 |
| Porosity (%) | 39 | 47 | 51 | 64 | 66 |
Porosity can be calculated with following formula:
η＝(1-P
1/P
0)×100％；
η represents the porosity of barrier film, P in the formula
1The apparent density of expression film, P
0The bulk density of expression fiber material.
If the spray flight lead changes from (shower nozzle and the distance that connects a cylinder are also referred to as and solidify distance) in the film-forming process, the electrospinning temperature also must be done suitable adjustment, makes to be sprayed onto to reach when connecing the silk tube, forms netted barrier film just.
Dimethyl formamide is the good solvent of PVDF, and acetone is poor solvent.If they are mixed use, porosity to film also has a significant impact, and is applying electric field strength 1000V/cm, and the spray flight lead is from 22.5cm, under 45 ℃ of conditions of electrospinning temperature, acetone and dimethyl formamide (DMF) ratio is as shown in the table to the influence that film forming causes in the solvent:
| Acetone: DMF (v: v) | Film thickness (μ m) | Porosity (%) |
| 1∶1 | 50 | 85 |
| 4∶6 | 55 | 71 |
| 3∶7 | 35 | 42 |
| 2∶8 | 40 | 39 |
In physics institute of Chinese Academy of Sciences solid state ionics laboratory, the lithium battery diaphragm that utilizes the present invention to produce is used for two electrode simulated batteries carries out the performance test experiment.Getting one of them typical sample result is expressed as follows:
Thickness of sample: 10 μ m porositys 38%
Test mode: two electrode simulated battery constant current pressure limitings, work electrode: LiNiCoMnO
2, to electrode: metallic lithium foil
Electrolyte: 1MLiPF
6, EC-DMC (1: 1)
Current density: 0.5C the last fortnight, 50 weeks behind the 2C, voltage range: 4.3-3.3V
Testing equipment: Land
Experimental result as shown in Figure 1, among the figure, the A sets of curves is the charging curve of battery, the B sets of curves for the discharge curve.As can be seen from the figure, the little electric current of the last fortnight discharges and recharges the high current charge-discharge curve with 50 weeks of back, has goodish repeatability, illustrates that the nano fibrous membrane internal resistance of cell is little.If the internal resistance of a battery is quite big, polarity effect is also big when discharging and recharging.External voltage raises soon when large current charge, and external voltage descends big during discharge.That is to say that if the internal resistance of cell is big, big electric current and little electric current charging and discharging curve can differ greatly.
We can illustrate with a relational expression:
V
2C＝V
0.5C-R(2C-0.5C)
V in the formula
2CAnd V
0.5CExternal circuit voltage when representing with 2C and 0.5C current discharge respectively, R is the internal resistance of cell.Obviously, if internal resistance R is big, if difference between current is big more, second of following formula is also big more, and the voltage of different electric currents can finely not overlap with capacity curve.In experiment, though used nanofiber membrane porosity has only 38%, because thickness has only 10 μ m, the internal resistance that is produced by barrier film remains very low.And obtain the barrier film of 10 μ m thickness with mechanical stretching method of the prior art, be unusual difficulty.
The experiment of assembling battery of mobile phone effect:
Utilize method of the present invention to prepare a collection of nanofiber lithium battery diaphragm, admittedly sharp power supply company of letter alliance assembling cellular li-ion battery experiment in department of chemistry of Fudan University and Beijing respectively.
One group of lithium battery of admittedly sharp power supply company of letter alliance assembling in Beijing, wherein two key property is listed in the table below:
Experiment condition is: the wide 46mm of film, long 600mm, thick 25 μ m, porosity 71%
| The film numbering | Anodal specific capacity performance mAh/g | Liquid absorption g | Charge and discharge efficient % first | Internal resistance m Ω |
| 1a | 139.8 | 3.703 | 86 | 36.4 |
| 1b | 138.3 | 3.557 | 89.3 | 37.8 |
Positive pole in the battery is LiMn
2O
4, its theoretical specific capacity 148mAh/g, actual 110-120mAh/g.This two battery is tested anodal specific capacity performance and has been improved 15%.
In one group of lithium battery of department of chemistry of Fudan University assembling, wherein a kind of typical results is with nanofiber film thickness 20 μ m, the sample of porosity 42%, and the assembling model is 0603450 lithium ion battery.This anode is LiCoO
2, negative pole is the modified natural graphite material, electrolyte is 1MLiPF
6+ EC/DEC/DMC through changing into, after sealing, carries out loop test.
At first, be charged to 4.2V, change constant voltage charge into, when electric current reaches 0.05A, stop charging with the 1.0A constant current charge.Spend 10 minutes, then from the 1.0A constant current discharge to 3.0V the circulation 400 times the result as shown in Figure 3.Solid line is represented the variation of each time circulation volume among the figure, and dotted line represents that the relevant mobile phone of country keeps level (80%) with 300 circulation volumes of lithium ion battery technical standard (GB/Y18287-2000).As seen from the figure battery first capacity be 1050mAh, 400 the circulation time the back capacity be 901mAh, conservation rate is 85%.Compare with national standard, use after the nanofiber lithium battery diaphragm of the present invention's preparation, battery life can improve more than 30%.
As implementing a kind of embodiment for preparing the equipment of lithium battery diaphragm of method of the present invention, as shown in Figure 3, by reservoir 1, shower nozzle 6, connect silk tube 7 and high-voltage D.C. generator constitutes; Reservoir 1 is divided into head tank 2 and Lower tank 3, links to each other by communicating pipe 4 between head tank 2 and the Lower tank 3, and Lower tank 3 links to each other with shower nozzle 6 by fluid flow tube 5; Shower nozzle 6 has a plurality of, and a plurality of shower nozzles 6 are arranged in a row or more; Connect the position that silk tube 7 is positioned near the spout of shower nozzle 6, the orientation of a plurality of shower nozzles 6 is parallel to the axis that connects silk tube 7; Connecing silk tube 7 can rotate along its central axis, and shower nozzle 6 can move back and forth along the axis direction that connects silk tube 7; The high-voltage output connector of high-voltage D.C. generator is connected on the shower nozzle 6; 8 is earth terminal.
The present invention makes back and forth movement with many jet head sets silk tube 7 that connects, and the electrostatic field of eliminating 6 in shower nozzle disturbs.A plurality of shower nozzles can be distributed as two rows, and every row is distributed with the syringe needle more than ten, shower nozzle internal diameter φ 0.3-0.8mm.Connect silk tube 7 and be diameter phi 200mm, the cylinder of long 500mm, cylinder rotates in many jet head sets vertical direction, to eliminate the electrostatic interference between two row's shower nozzles.After eliminating the electrostatic field interference, can make uniform lithium battery diaphragm.The distance of jet head sets back and forth movement and frequency connect a rotating speed of tube 7, can regulate as required and set.Generally jet head sets back and forth movement speed is 1-10 time/minute, connects rotating speed 1-10 rev/min of silk tube 7.
The present invention has adopted the method for head tank and Lower tank associating feed flow, with the pressure reduction feed flow of liquid.Electrospinning liquid flows into Lower tank from head tank.Fluid flow tube of design is constant with the pressure reduction that keeps liquid on Lower tank.Regulate fluid flow tube and jet head sets height, the flow of scalable electrospinning liquid.
Claims (5)
1, a kind of preparation method of lithium battery diaphragm may further comprise the steps:
1) preparation electrospinning liquid: prepare solvent by following mass percent: dimethylformamide: 70% ~ 90%; Acetone: 10% ~ 30%; Be that solute adds the above-mentioned solvent for preparing then with the Kynoar, mass concentration is 7% ~ 10%;
2) the electrospinning liquid of preparing in the step 1) is put into reservoir, under 30 ~ 45 ℃ of ambient temperatures, at shower nozzle and connect the electric field that adds 1000 ~ 2000V/cm between the silk tube, utilize shower nozzle that electrospinning liquid is sprayed onto and connect on the silk tube, form the electrospinning cortina connecing on the silk tube;
3) regulate the evaporation rate of solvent in the electrospinning temperature control electrospinning liquid, when electrospinning liquid being arrived connect the silk tube, can form reticular membrane connecing on the silk tube just.
2, the preparation method of lithium battery diaphragm according to claim 1 is characterized in that, the mass concentration of described electrospinning liquid is 8%.
3, the preparation method of lithium battery diaphragm according to claim 1, it is characterized in that, in described step 2) in, the ambient temperature when keeping spinning is constant, controls the porosity of the lithium battery diaphragm that makes by the ratio between dimethylformamide and the acetone in the adjusting electrospinning liquid solvent.
4, the preparation method of lithium battery diaphragm according to claim 1, it is characterized in that, in described step 2) in, keep the proportions constant between the dimethylformamide and acetone in the electrospinning liquid solvent, control the porosity of the lithium battery diaphragm that makes by the ambient temperature of regulating spinning.
5, a kind of equipment that is used to prepare lithium battery diaphragm is characterized in that, comprises reservoir, shower nozzle, connects silk tube and high-voltage D.C. generator; Described reservoir is divided into head tank and Lower tank, links to each other by communicating pipe between described head tank and the Lower tank, and described Lower tank links to each other with described shower nozzle by fluid flow tube; Described shower nozzle has a plurality of, and described a plurality of nozzle tip arrangement become at least one row; The described silk tube of connecing is positioned at position near the spout of shower nozzle, and the orientation of described a plurality of shower nozzles is parallel to a described axis that connects the silk tube; The described silk tube that connects can rotate along its central axis, and described shower nozzle can move back and forth along connecing wire tube shaft line direction; The high-tension current out splice going splice of described high-voltage D.C. generator is connected on the described shower nozzle.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100654299A CN101038959A (en) | 2007-04-13 | 2007-04-13 | Method and equipment for preparation of lithium battery diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100654299A CN101038959A (en) | 2007-04-13 | 2007-04-13 | Method and equipment for preparation of lithium battery diaphragm |
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| CNA2007100654299A Pending CN101038959A (en) | 2007-04-13 | 2007-04-13 | Method and equipment for preparation of lithium battery diaphragm |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101586268B (en) * | 2009-06-25 | 2011-01-05 | 天津大学 | Core-shell structured polyvinylidene fluoride/polycarbonate superfine fiber and preparing method thereof |
| CN102218871A (en) * | 2011-04-14 | 2011-10-19 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102600999A (en) * | 2012-03-02 | 2012-07-25 | 余姚市百立嘉电子有限公司 | Manufacturing method and device of sprayed film of lithium battery |
| CN102668172A (en) * | 2009-11-23 | 2012-09-12 | 株式会社Lg化学 | Method for preparing separator having porous coating layer, separator formed therefrom and electrochemical device containing same |
| CN107151823A (en) * | 2017-05-22 | 2017-09-12 | 苏州大学 | Electrostatic spinning apparatus |
| CN109378429A (en) * | 2018-10-20 | 2019-02-22 | 武汉惠强新能源材料科技有限公司 | The temperature control equipment of battery diaphragm production line |
-
2007
- 2007-04-13 CN CNA2007100654299A patent/CN101038959A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101586268B (en) * | 2009-06-25 | 2011-01-05 | 天津大学 | Core-shell structured polyvinylidene fluoride/polycarbonate superfine fiber and preparing method thereof |
| CN102668172A (en) * | 2009-11-23 | 2012-09-12 | 株式会社Lg化学 | Method for preparing separator having porous coating layer, separator formed therefrom and electrochemical device containing same |
| CN102218871A (en) * | 2011-04-14 | 2011-10-19 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102218871B (en) * | 2011-04-14 | 2014-08-27 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102600999A (en) * | 2012-03-02 | 2012-07-25 | 余姚市百立嘉电子有限公司 | Manufacturing method and device of sprayed film of lithium battery |
| CN107151823A (en) * | 2017-05-22 | 2017-09-12 | 苏州大学 | Electrostatic spinning apparatus |
| CN109378429A (en) * | 2018-10-20 | 2019-02-22 | 武汉惠强新能源材料科技有限公司 | The temperature control equipment of battery diaphragm production line |
| CN109378429B (en) * | 2018-10-20 | 2023-10-13 | 武汉惠强新能源材料科技有限公司 | Temperature control device of battery diaphragm production line |
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